New compositions of matter



Lsidne B. Richter, Chicago, 111., assignorto Velsicol .Y is selectedfrom the group consisting of bromine and Bi- 1 Br Br 1 .in that theycontain a halogenated bicyclo (2.2.l) -heptene serious problems,attacking plants, leather, and many (11 oi 01 o 2 l,2,3,4,7,7-hexachloro-5-(a-thiocyother items of importance. The control of these or- 55gg ym )-blcyelo (2.2.l)-2-hepganisms has proven to be a difficult thingdue'to the 01 C1 C1 1 i i,2,3, i,7,7-hexachr -5-( t y -amany types offungi and the inability of known fungitoxic iiiigi-g-li c gt itr isubstances to completely control all of the known species. Cl oi G1 0 01,2,3,%,7 ,7 1 1 x c hio1- gbu nggyg g Consequently, there isconsiderable need for new and Br Br 9 12 ggfffig gj fi g betterfungicides.

United States Patent 0 "ice can best be attributed to the novelstructure of said compositions. 2,909,458 The new compositions of thepresent invention can be prepared as shown by the following equations,using the NEW COMPOSITIONS 0F MATTER 5 definitions of X, Y, Z, n and mas previously indicated:

Chemical Corporation, Chicago, 111., a corporation of Y llllllols Y l(CH ),.OH

No Drawing. Application July 1, 1957 10 I H (cmrnmi onooon Serial No.668,898

"11 Claims. (Cl. 167-30) [A] [B] Y 01 This invention relates-to newcompositions of matter. 15 Y I (G i)n0-0'-iJH(ommmn) In particular, thisinvention relates to new thiocyanate H esters containing a halogenatedbicyclo .(2.2.1)-heptene Y configuration. a C

It is an object of the present invention to prepare new, 1 .valuablethiocyanates. Y 0 C1 It is also an .object of. the present invention toprepare Y I g new compositions possessing fungitoxic properties. XOZ vNH SCN Another object of the present invention is the devising Y l i ofa new method for protecting matter against undesirable Y fung [Cl [D1Still another ob ect of the present invention is a new Y 0 method forthe control of plant pests.

Other objects of the present invention will become Y L g H2)" O C([)H(C"'H2m 1) apparent from the ensuing description. g Y SCN The newcompositions of the present invention are re- 1 presented by thefollowing structural formula: [E]

, Y E? In accordance'with these equations, the following table Y i -(Ci),.0-OoH(omHzm+,) illustrates the desired thiocyanate product: i H SONTABLEI Y l H2 Structure I Y X Z n 112 Product wherein X and Z areindependently selected from the 01 01'0110 group consisting of hydrogen,bromine and chlorine; each 1,2,3,4,7,7-hexachloro 5methylthioeyanoacetate-bicyclo (2.2.1)-2-heptene. 1,2,3,4,7 ,7-hexabromo5 methyltliio- 1 chlorine; n is selected from the group consisting of 0cyanoacetate'bicyck tene. I and integers from 1 to 14; m is selectedfrom the group 01 H H 1 0 1,2,3,4-tetrabro mo-5-methylthiocyconsistingof 0 and integers from 1 to 14. 5 anoaceme'bmyclo 4 Br H H 1 0Particularly of interest are the compounds represented 01 C1 01 0 l bythe above structure wherein each Y and X is chlorine. It can be seenthat the compounds wherein n is from 0-3 c1 oi 01 2 l4 and m from 0-3are likewise of more practical interest.

The compositions of the present invention areunique G1 G1 01 14 3 Do.1,2,3,4,7,7 hexachloro 5 (on thiocyanopropionate) bicyclo (2.2.1) 2

configuration in addition to the thiocyanate group. 01 O1 01 2 1 Fungusgrowth has proven itself to be one of the morea-thiocyanomyristatel-bicyelo I (2.2.l)-2-hepteue. UneXpectedlyiappllcant found lhfit P 110961 Br ,Br Br 14 0l,2,3,4,7,7-l1exabromo-5-(M-tetradeccompounds are excellent fungicides.This Is quite surpris- 31 1 tggi rg igoacetate) bic clo ing in view ofthe literature which indicates that monothio- Br Br Br 0 2 l,2,?i,7,7-hexabromo 5 (a'thiocyanobutyrate)-bicyclo (2.2.1)-2-heptene.l,2,3,4-tetrachloro 5 (4-butylu-thiocyanopalruitate)-bicyclo (2.2.1) 2lieptene.

cyanates (those compounds containing only one SCN group) are relativelyweak fungicides. The reason for 01 H H .14 this unusual propensity ofthe compounds of the present invention is not clearly explainable,particularly in view 1 01 H H T 1 BA- a of the fact that other compoundscontaining the halO- E"2.2. f ili%%? bicyclo genated bicyclo(2.2.l)-heptene configuration and which 0 H H 8 4 1,2,3,4-tetrach1oro-5;(soety are highly valuable commercial insecticides are not figg gggf m1,2,3,4-tetrabromo 5 (methyl-a-thiocyanobutyrate)-bieyclo (2.2.1) 2heptene.

especially good fungicides. Thus'is appears that these Br H H 1 2filiigitoxic characteristics of these new monothiocyanates Product1,2,3,4-tetrabrmo (S-pentyI-a-thiocyanopalmitate)-bicyclo (2.2.1)-2-heptene. 1,2,3,4-tetrabromo 5 (S-OCiJYl-a-thlogyanoacetateybicyclo(2.2.1)-2-hep- 1,2,3,4-tetrabromo 5(G-heXyI-a-thlocyauomyristate)-blcyclo (2.2.1)-2- heptene.

1,2,3,4,5-pentachloro 5 (methyl-athiocyanoproplonate)-biccylo(2.2.1)-2-heptene. A

1,2,3,4,5-pentachloro 6 thiocyanoacetate-bicyclo (2.2.1)-2-heptene.

l,2,3,4,5-pentachloro -5 (fi-hexyl athiocyanopalmitate)-bicyclo (2.2.1)-Z-heptene.

l,2,3,4,5-pentachloro 5 (methyl a thiocyanobutyrate)-bicyclo (2.2.1)-Z-heptene.

1,2,3,4,5-pentachloro 5 (pentyl a thiocyanobutyrate)-blcyclo (2.2.1)-Z-heptene.

1,2,3,4,5-pentabromo 5 (heptyl 0:

thiocyanopalmitate)-blcyclo (2.2.1)- 2-heptene.

l,2,3,4,5-pentabromo 5 (propyl a thiocyanoacetate)-bicyclo (221)-2-heptene.

1,2,3,4,5-pentabromo 5 (butyl-a-thiocyanovalerate)-bicyc1o (2.2.1) 2heptene.

1,2,3,4,5-peutabromo 5 (tetradecanyl-a-thiocyanobutyrate) bicyclo(2.2.1)-2-heptene.

1,2,3,4,5-pentabromo 5 (methyl a thiocyanopropi0nate)-b1cyclo(2.2.1)-2-heptene.

mum

Cl C1 Cl C1 The following examples describe in detail the preparation ofthese new compositions. These examples utilize the previously shownreaction; however, the mode of preparation is notcritical and othermethods may be used to prepare the compositions of the presentinvention.

The starting material for this two-step process, indicated as [A], ispreparable by the Diels-Alder adduction of tetra-, penta-, orhexahalocyclopentadiene and a-monoolefinic w-monohydroxyalcoholscontaining from 3-16 carbon atoms at a temperature between about 100 C.and 180 C. Since vinyl alcohol is not stable when it is desired that nin the equations be 0, it is necessary to adduct with vinyl acetate andhydrolyze the adduct to prepare the present compositions wherein n is 0.The following alcohols are included:

Allyl alcohol Propenol-2 1-butene-4-ol l-pentene-S-ol l-hexene-G-ol1-heptene-7-ol l-octene-S-ol 1-nonenc-9-ol l-decene-lO-ol1-undecene-11-ol l-dodecene-lZ-ol 1-tridecene-13-ol 1-tetradecene-14-olIn accordance with this process for the preparation of the presentcomposition, the above indicated Diels-Alder adducts ofhexachlorocyclopentadiene and u-mOnO- olefinic-w-monoalcohols arereacted with one of the following a-chloroacids:

a-Monochloropropionic acid a-Monochlorobutyric acid m-Monochlorovalericacid a-Monochlorocaproic acid u-Monochlorooenanthic acida-Monochlorocaprylic acid a-Monochloropelargonic acid a-Monochlorocapricacid a-Monochloroundecoic acid a-Monochlorolauric acida-Monochlorotridecoic acid cc-MOIIOChlOl'OIIlYIiSfiC acida-Monochloropentadecoic acid a-Monochloropalmitic acid This reactionwhich results in the intermediate denoted as [C] in the previousreaction equations can be performed using benzene or toluene as solvent,at atmospheric pressure as a continuous or batch process, attemperatures between about 50 C. and C., with satisfactory yieldsobtainable in from about 1 to 10 hours of reaction, the productrecoverable by distillation of said mixture.

The final step in this process for the preparation of the presentinvention is the reaction of the chloride [C] in the reaction equations,with ammonium thiocyanate, a reaction which yields the new thiocyanateester of the present invention. This reaction is conveniently performedwith alcohol as the solvent, under atmospheric pressure at from about50-150" C. for about 1 to 20 hours. The product is-recovered bydistillation of the reaction mixture.

The following examples describe this preparation of the presentcompositions of matter.

Example I PREPARATION OF 1,2,3,4,7,7-HEXACHLORO-5-METHYL-HYDROXY-BICYCLO (2.2.1) -2HEPTENE Hexachlorocyclopentadiene (136.4grams; 0.5 mol) was placed in a three-necked glass reaction vesselequipped with stirrer, thermometer, addition funnel, reflux condenserand heated to about 160 C. Allyl alcohol (348 grams; 0.6 mol) was addeddropwise from the addition funnel over a five-hour period, maintaining atemperature between about -165 C. The solution was cooled, added topentane (500 mL), and the resulting product obtained by filtration wasrecrystallized from hexane, yielding 101 grams of product having a MP.of 162.0-162.5 C. The product was analyzed for C, H and Cl.

Theoretical .Q

29. 04 1. ound 1 Example II PREPARATION OF1,2,3,4,7,7-HEXACHLORO-5-METHYL- CHLORO-ACETATE-BICYCLO(2.2.1)-2-HEPTENE 1,2,3,4,7,7-heXachloro-5-methylhydroXy-bicyclo(2.2.1)- Z-heptene (99.2 grams; 0.3 mol) was placed in a threeneckedglass reaction flask equipped with stirrer, thermometer, Dean-Starketube and reflux condenser and containing toluene (200 ml), chloroaceticacid (28.4 grams; 0.3 mol) and p-toluene sulfonic acid (1 gram). Thesolution was refluxed for 5 hours, then cooled to room temperature,washed with bicarbonate, and dried over calcium chloride. The solventwas removed under reduced pressure and the product recovered bydistillation as the fraction with boiling point of 139140 C at 0.15 mm.Hg pressure and a refractive index at 24 C. of 1.5487. An elementalanalysis for C H Cl O was Theoretical Found 60. 94

Example III reflux condenser and containingfethylalcohol .(5 -m1.), 3iammoniumv thiocyanoacetate. (19 grams; 0.25 ,.n1o1) (;was added andthesolutionrefluxdwith stirring for.,l6 hours. At the end. of,the.f16.-hour period, the solution was cooled to room'temperature, filtered,and the'isolvent. removed under reduced .pressure. fIfhe desired productwas obtained. by molecularldistillation of..t1i e reaction mixture at0.2 .mm. pressure and tempera tures of 145-155" .C. Itslre fractiveindex at..24 C. was

Example V. I

PREPARATION OF 1,2,3,4=,7,7-HEXACHLORO--(METHYL- Q-C ILOnOP I NAT rcrcno2.2.1)-2-HEPTEl lE Product of Example I (99.2 grams; 0.3 mol) is placedin a three-necked glassreaction flask equipped with stirrer,thermometer, and reflux condenser and containing toluene (200 ml.),u-chloropropionic acid (32.6 grams; 0.3 mol) and p-toluene sulfonic acid(1 gram). The

solution is refluxed for 5 hours,-cooled.tozroom tempera. ture, washedwith bicarbonate, and driedovercalcium.

chloride. The solvent is removed under reduced pressure and the desiredcompound is recovered by distillation.

., Exa l PREPARATION OF 1,2,3,4,7,7:HEXACHLORO-5.-(METHYL a..THIOOYANOPROPIONA E) BICYCLO (2.2.1)- 2-HEP- TENE 1,2,3,4,7 ,7hex-achloro 5 (methyle pionate)-bicyclo (2.2.1)-2-propionate(96.7 grams;0.23 mol) is placed in a three-necked. glass reaction vessel equippedwith stirrer, thermometer and reflux condenser. and containing ethylalcohol-.(500,ml.-). v Ammonium:

thiocyanoacetate (19 grams; 0.25 mol) was added and the solutionrefluxed with stirring for 16 hours. At the. end of the 16-hour periodthe solution was cooled to room temperature, filtered, and the solventremoved under reduced pressure. Thedesired product is obtaine d by.molecular distillation oi the reaction mixture and its structure is: i

(1 I on oJi-ou-oH.

- soN Ewan...

PREPARATION OF 1,2,3,4,'m-nnxAonLo-no-s-nrnrtoxr- BICYCLO .(2.2.1)- 2'HEPTENE This composition .usable as an intermediate in thepreparationof the compositions of the present invention is equivalent to theDiels-Alder adduct or hexa'chlorocyclopentadiene and vinyl alcohol.Since vinyl alcohol is not stable, the following two-step process isused.

Hexachlorocyclopentadiene (163.4 grams; 0.6 mol) was placed in a glassreaction vessel equipped with stirrer,

' thermometen'reflux condenser and sparger. Thehexachlorocyclopentadiene was placed in a glass reaction vessel equippedwith stirrer, thermometer, reflux condenser and sparger. Thehexachlorocyclopentadiene was heated to 180 C. and vinyl.acetate (51.7grams;0. 6: mol) was added through the sparger below the surface of theheated addition.

180 C. for an additional hour after, completion of the covered byrecrystallization from hexane. Its melting point was 44.5-46.0 C.

The above prepared Diels-Alder adduct of hexachlorocyclopentadiene andvinyl acetate (108.3 grams; 0.3 mol) was placed in a reaction vesselequipped with stirrer, thermometer and reflux condenser and containingmethanol (64 grams; 2.0 mol) and hydrochloric acid- (73.0 grams; 2.0mol). The mixture was held for 2 hours at 120 C. The product recoveredby filtration has amelting point of 1520-1525 C.

1. Example VII PREPARATION OF 1,2,3',4,7,7-HEXACHLORO-5-(ti-CHLO-ROPROPIONATE -BICYCLO (2.2.1 -2-HEPTENE 1,2,3,4,7,7 hexachloro5-hydroxy-bicyclo (2.2.1)-2-heptene,( 98. l grams; 0.3 mol) .is placedin a glass reaction vessel equipped with stirrer, thermometer,Dea'n-Starke tube, and reflux condenserand containing toluene (200 ml.)a-chloropropionic acid (28.4 grams; 0.3 mol) and p-toluene sulphonicacid (1 gram). The solution is refluxed for 5 hours, then cooled to roomtemperature, washed with bicarbonate, anddried over calcium chloride.Thejsolvent is removedunderreduced pressure and the desired productrecovered by distillation.

Example VIII PREPARATION OF 1,2,3,4,7,7-HEXACHLORO-5 (a-THIO-CIYANOIROPIONATEMBICYCLO (2.2.1)-2-HEPTENE 1,2,3,4,7,7 hexachloro, 5 (a;chlorocyanopropionate) -bicyclo (2.2.1)-2-heptene (94.0 grams; 0.23mol) is placed in a three-necked glass reaction flask equipped withstirrer, thermometer and reflux condenser, and containing ethyl alcohol(500 ml.). Ammonium thiocyanate (19 grams; 0.25 mol) is added and thesolution refluxed with stirring for 16 hours. At the end of the 16-hourreaction period, the reaction mixture is cooled to roomternperature,filtered, and the solvent removed under reduced pressure. The desiredproduct is Obtainedby molecular distillation and has the followingstructural formula:

for 5 hours, then cooled to room temperature, washed with bicarbonate,and dried over calcium chloride. The solvent is. removed under reducedpressure and the desired product recovered by distillation.

s M Example X. I PREPARATION .OF 1,2,3,4,7 ,7 -.HEXACHLORO-5-(THIO-CYANOACETATE -BICYCLO (2.2.1 -2-HEPTENE 1,2,3,4,7,7 hexachloro 5.-- achloroacetate-bicyclo (2.2.1) 2- heptene (90.5 grams; 0.23 mol) isplaced in a three-necked glass reaction vessel equipped with stirrer,thermometer and reflux condenser and containing ethyl alcohol (500 m1).Ammonium thiocyanate (19 grams; 0.25 .mo1) is added-and the solutionrefluxed with stirring for 16 hours. At the end of the 16-hour reactionperiod,

Then unreacted hexachlorocyclopentadiene was removed by steamdistillation and the product rethe reaction mixture is cooled to roomtemperature, filtered, and the solvent removed under reduced pressure.The desired product is obtained by molecular distillation and has thefollowing structural formula:

n l 01 L OCCSGN I01 01 H .1, CI l H2 Example XI PREPARATION OF1,2,3,4,7,7HEXACHLORO-5-(HEPTYL- I 6-OL)-BICYCLO (2.2.1)-2-HEPTENEHexachlorocyclopentadiene (136.4 grams; 0.5 mol) is placed in athree-necked glass reaction vessel equipped with stirrer, thermometer,addition funnel and reflux condenser and heated to about 160 C."1-octene-8-ol (76.8 grams; 0.6 mol) is added dropwise from the additionfunnel over a five-hour period, maintaining the temperature at about 160C. The solution is cooled, added to.

pentane (500 ml.) and the desired product obtained by filtration.

Example XII PREPARATION OF 1,2,3,4,7,7-HEXACHLORO-5-(HEPTYL- a-CHLOROCAPRYLATE -BICYCLO (2.2.1 -2-HEPTENE 1,2,3,4,7,7 hexachloro 5 (heptyl 6ol) bicyclo (2.2.1)-2-heptene (120.3 grams; 0.3 mol) is placed in athree-necked glass reaction vessel equipped with stirrer, thermometer,Dean-Starke tube and reflux condenser and containing toluene (200 ml.),a-chlorocapyrlic acid (53.6 grams; 0.3 mol) and p-toluene sulphonic acid(1 gram). The solution is refluxed for five hours, then cooled to roomtemperature, washed with bicarbonate and dried over calcium chloride.The solvent is removed under reduced pressure and the product recoveredby distillation.

Example XIII PREPARATION OF 1,2,3,4,7,7-HEXACHLORO-5-(HEPTYL- aTHIOCYANOCAPRYLATE) BICYCLO (2.2.1 2 HEP- TENE As previously indicated,the present compositions of matter have superior fungus toxicity, makingthem quite valuable in the protection of numerous items, such as plantlife, leather and other matter susceptible to attack by various fungi.

Indicative of this valuable property of these new, unique compounds isthe following fungicidal test using the glass slide spore germinationmethod:

Example XIV A measured concentration of spores of Schlerotiniafructicola was placed on glass slides in contact with the statedconcentration of 1,2,3,4,7,7-hexachloro-5-methylthiocyanoacetate-bicyclo(2.2.l)-2-heptene prepared by dissolving said test compound in acetoneand dispersing the solution in water. The percent germination of thespores wasthen determined after 24 hours incubation at 72 F. At aconcentration of 100 ppm. the percent germinationwas found to be 1%.. Ata concentration of 10 ppm, the .percent germination was 38%. Thus, theED value for said test compound is less than 10 These compositions canbe used by .means known to the art for the application of fungicides andother like materials. Thus, they can be dissolved in a suitable solvent,such as toluene, and sprayed onto the material or land to be protected;or they can be formulated with an inert carrier material, ground to adesired particle size, and dusted onto the area; or they can beformulated into emulsifiable concentrates, dispersed in water, and thematerial to be protected dipped therein. 'Likewise,'other ingredients,such as stickers, wettingagents, dispersing agents, and the like, can'be formulated therewith. If desired, these compositions can beincorporated into waxes, etc. and may be formulated in combination withother fungicides, insecticides, herbicides so that the user thereof canprovide his material with this additional benefit. The

following formulations are merely illustrative, and of course do not, aspreviously indicated, exclude various other ingredients.

Example XV I Percent by weight Product of Example VIII 50 Celite 209 50Celite 209 is a diatomaceous earth utilized as a relatively inertcarrier. The composition represented here is a 50% dust or granular,depending on the degree of grinding, if any, performed on theformulation, and is applied by dusting, spreading, etc., to control suchplant diseases as Phytophthora infestans and Alternaria solani.

Example XVI Percent by weight Product of Example X 70 Micro-Cel 800 27Triton X-l00 3 Product of Example XIII Isopropyl acetate 23 Isopropylalcohol 10 Atlas G-1690 7 Atlas 6-1690 is a commercially availableemulsifier. This formulation is an emulsifiable concentrate readilyusable for spraying the plant or other material to be protected againstsuch diseases as venluria inaequalis (apple scab), leaf spots, cerealand apply rusts and other fungi. In addition to the above indicatedutility of the present compositions, they are likewise valuable asintermediates in the preparation of many valuable compounds. Thus,

for example, they can be reacted with thio acids to form esters of thethio acid; with chlorine to form chlorosulfones and other like generalreactions of thiocyanates.

I claim:

Y i? Y i #0112 ,,-0-CGH(CmHzm-1-1) 'x z n SON Y H:

wherein X and Z are independently selected from the group consisting ofhydrogen, chlorine and bromine;

9 each Y is selected from the group consisting of bromine and chlorine;m and n are each selected from the group consisting of and integers from1 to 14.

wherein X and Z are independently selected from the group consisting ofhydrogen and chlorine; m and n are each selected from the groupconsisting of 0 and integers from 1 to 14.

wherein m and n are each selected from the group consisting of 0 andintegers from 1 to 14.

01 01 i L 0-23-0125 01 O1 SIGN (J11 H:

01 01 l o-0-0H-0H,

9. The method for the control of undesirable fungus growth whichcomprises applying to the material being protected an efiective quantityof the composition of claim 1.

10. The method for the protection of material from fungus whichcomprises contacting said material with an efiective quantity of thecomposition of claim 1.

11. The process for the control of fungus which comprises theapplication of an efiective amount of the composition of claim 1 totheir environment.

References Cited in the file of this patent UNITED STATES PATENTS2,217,613 Borglin Oct. 8, 1940 2,217,614 Borglin Oct. 8, 1940 2,616,825Gilbert Nov. 4, 1952 2,638,431 Harry May 12, 1953 2,650,240 Olin Aug.25, 1953 2,744,924 Herzfeld May 8, 1956 UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Patent No 2,909,458 October 20, 1959 Sidne; BRichter It is hereby certified that error appears. in the printedspecification of the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below;

Column 2, line 44, in Table I, sixth column thereoi, for tetrabromo read-tetrachloroline 45, same Table I, same sixth column thereof, for "do.read 1,2 ,3 ,4 tetrabromo 5 -methylthiocyanoacetate-hicyclo(2.2.1)- Z heteneo column 3, line 13, in Table l Continued, sixth column thereof, for-==bicoylo" read an hicyclo .Signed and sealed this 26th day of April1960..

Attest:

ROBERT C. WATSON KARL Ho AXLINE Attesting Oflicer Commissioner ofPatents

9. THE METHOD FOR THE CONTROL OF UNDESIRABLE FUNGUS GROWTH WHICHCOMPRISES APPLYING TO THE MATERIAL BEING PROTECTED AN EFFECTIVE QUANTITYOF THE COMPOSITION OF CLAIM 1.